Derivatives of certain highly branched chain acids as coating aids



United States Patent Ofifice 3,165,409 Patented Jan. 12, 1965 3,165,409DERIVATIVES OF CERTAIN HIGHLY BRANCHED CHAIN ACIDS AS COATING AIDSWilliam J. Knox, Jr., Rochester, N.Y., and Robert E. Sticker, Lawrence,Kama, assignors to Eastman Kodak Company, Rochester, N.Y., a corporationof New Jersey N Drawing. Filed Feb. 7, 1962, Ser. No. 171,560 11 Claims.(Cl. 9694) This invention relates to coating aids for gelatin coatingsolutions particularly for photographic purposes which are certainalkaryloxyalkanoyl.taurine salts.

In the application of aqueous gelatin coating compositions, particularlygelatin-silver halide photographic emulsions, to a support such as filmbase or paper, it is desirable that there be present therein a coatingaid to facilitate the application of the layer to the support. Thisapplication of gelatin composition can be either as a single layer or inmultilayers such as by simultaneous application. The presence of coatingaid reduces defects such as repellencies, pencil line streaks, and thelike in the coating when dry. In such coating operations, however, thecoating aids used often fail to induce adequate rewettability of thelayer which usually exhibits surface slickness. In many cases, thissurface slickness or slipperiness is especially undesirable in certainphoto graphic products because of difficulties in handling and possibletelescoping of the film wound in the form of rolls. Often it has beennecessary to use a mixture of two surfactants as the coating aid toimpart both desired surface roughness and rewettability of the drycoating. Not onlyis the mixing of coating aids sometimes bothersome butin addition some of the surfactants proposed for that purpose arenaturally occurring materials and may vary in quality or containimpurities undesirable for photographicuse.

One object of our invention is to provide gelatin coating compositionsfrom which layers having both adequate rewettability after drying-andsufiicient roughness of surface to facilitate handling may be obtained.Another object of our invention is to provide gelatin coatingcompositions from which coatings having few if any repellencies, pencilline streaks or other undesirable defects may be obtained. A furtherobject of our invention is to provide coating aids comprising certainsynthetically prepared taurines. Other objects of our invention willappear herein.

We have found that taurines which have alkaryloxyalkanoyl substituentsshow good properties when incorporated in photographic emulsions orother gelatin coating compositions as coating aids. The resultingcompositions have provided coatings having good handlingcharacteristics. Coating aids which we have found to be particularlyuseful in gelatin compositions are those having the formula:

8 to 16 carbon atoms, n is an integer 1 or 2, Q is a bond or R is alkylof 1 to4 carbon atoms or cycloalkyl, and

M is a substituent such as Na, K, Li, NH or alkylammonium to give awater soluble salt.

We have found that when these compounds are incorporated in smallamounts in gelatin coating compositions those compositions exhibit goodcoating properties. This has been found to be true both in coatingoperations in which a single-layer has been applied to a support or inmultiple coating'operations such as described in US. 2,761,991 of T. A.Russell. It was found that any amount of coating aid present in thegelatin composition was effective in giving better coatings but that itis especially convenient to operate within the range of 05-15%, based onthe weight of the gelatin, of coating aid in the composition andpreferably within therange of 110%. In the coating aids in accordancewith our invention it is preferred that the branched alkyl substituentattached to the benzene ring have 8-16 carbon atoms although includedwithin our invention are the coating aids'in which two alkylsubstituents may be on the benzene ring, the sum of the carbons of thesealkyls being 8-16 carbon atoms. For instance, some of the compoundswhich have been considered most convenient to use are alkaryl compoundsin which the sum of the alkyl substituents of the alkaryl has 8, 10, 12,15 or the like carbon atoms either one or two alkyls being attachedto'the benzene ring. The nitrogen of the taurine compound has as asubstituent thereon alkyl of 14 carbon atoms such as methyl, ethyl orcycloalkyl i.e. cyclohexyl.

Some coating aids for use in gelatin coating compositions in accordancewith our invention are:

Nasalt of N-p-t.-octylphenoxyacetyl-N-cyclohexyltaurine Na salt ofN-p-t.-octylphenoxyacetyl-N-methyltaurine Na salt of N-p-t.-octylphenoxyacetylglycyl-N-methyltau- -r1ne Na salt ofN-(branched)nonylphenoxyacetyl-N-methyltaurine i 4 Na salt ofN-(branched)nonylphenoxyacetyl-N-cyclohexyltaurine Na salt ofN-(branched)dodecylphenoxyacetyl-N-methyl-' taurine Na salt ofN-(branched)dodecylphenoxyacetyl-N-cyclohexyltaurine Na salt ofN-(branched)dodecylphenoxyacetyl-N-ethyltaurine The following examplesillustrate the preparation of coating aids ofthe type referred to andtheir use in preparing film products.

Example 1 354 parts (0.359 mole) of a 23.8% aqueous solution' of thesodium salt of N-cyclohexyltaurine was evaporated in vacuo on a steambath to /s /2 the original volume so as to remove any cyclohexylaminewhich might be present. The mass was then diluted withwater to 354 partsand 200 parts of acetone were added. Added simultaneously to the stirredsolution at 60 C. while emulsion layer and a clear gelatin overcoatingwere apaids was used so as to give both good developer spread andresistance to slipping. The following results were obtained:

two ethereal extracts were combined, dried oversodium sulfate, andfiltered. The ether was mostly evaporated off at room temperature;further evaporationwas then carried out at 80 C. for several days,followed by evaporation in vacuoat 55 C." The light tan'product thus ,5surfaqtantconcentration Dr 1 O f f 1 GI 06 0 e e 81101 obta ned, N p.-t. octylphenoxyacetyl N cyclohexyl- V gg g Friction 7 2 m taurine,sodium salt, was useful as a coating aid in aque-: Wet Emui, wotOvercoat, ous gelatin compositions. g

Exampl 2 V 0.13 0.5 g. gone 0.25 0.5 one 1690 arts 4.2 moles of a 40%solution in water of 5 8,55 7 n 0 5 N the sodium salt ofN-methyltaurine' Was evaporated 111' standard St 17 7 9 vacuo on a steambath to approximately /2 the original volume thereby removing anymethylamine present. The masswas diluted to 1690 parts with Water andwas further 15 diluted with 6000 parts of 1:2 acetonezwater. 1185 partsmoles) of p c y p y y chloride and 168 carrying a clear gelatin overcoatandthe area which devel0ps Parts 25% sdium t added if); iri tiv iy niiififsio l ioififiiiii zt tin g iififii fii multaneously to thethestllfred solutlon at 600 "Whlle wet. A developer spread of 4.0 em. ormore is desirable. maintaining a PH The t having been Si(ififiifiigaiffiifi ieiiiii iil r iiififiTfifi completed, the reactlon'masswas surfed for one 110111 at gelatin overcoat against the uncoated sideof a similar sheet. renlwing .aceto-ne and a The iii}? iiiii fiiis f 231551? c ofii'i s iiiiiiiifiglioiiiii fitfi tlon s shghfly turbldbutcleared p dllutlon to Difficulties occur in stacking coated sheets ifthe coefficient concentration and coolingto room temperature. Thevffliction'is lessihwl flb011t0-25- material,N-p-t.-octylphenoxyacetyl-N-methyltaurine, so- E l 7 dium salt, wasfound to impart good coating properties to gelatin coating compositionsin which it is incorporated as will be indicated below.

NOTE-I11 the above tables repellencies are the number of dull anduncoated spotsin the area referred to.

1 Developer spread is determined as follows One cc. of developersolution is delivered-i a. standard manner to a surface ofphotographically sensitized paper In a coating experiment similar tothatdescribed in the preceding example, N-p-t.-octylphenoxyacetyl Ncyclohexyltaurine, sodium salt (OPCT), was used as the coat- Example 3 0ing aid. The following results were obtained:

In a coating experiment in which a single coating of an aqueous solutionof gelatin was applied to cellulose ace- Surfactant Cmmentmim fggg ofRepenencies tate film base .N-p-t.-octylphenoxyacetyl-N-methyltaurine,Wet W et Overcoat 3111. Friction (7.5'sq. ft.) sodium salt (OPT), wasused as the coating aid at aconym, m i centration of 0.22 gram per poundof gelatin solution. I V g t The following results were obtained ascompared with-a g- 8-2 3g 8- V control in which no coating aid was used:0Z5 015 16:60 f 02627 None Repellencies Standard Standard 8.04. 0.715None Coating aid: (25 ft.)

Control 13 40 j a p 8 OPT 2.

Example4 In a coating run similar to that described in Example 3 exceptthat N-pentadecylphenoxyacetyl-N-methyltaurine,

ample 3, N-p-t.-octylphe ioxyacetyl-N cyclohexyltaurine,

following results were obtained:

sodium salt (PPT), was used as a coating aid, the follow- Repel-Longiing results (as compared with a control in WhlCh no coat- CoatingAid I lencies Meme tudmal ing aid was used) were obtained: a a streaks.

. RQPQL Longi Control 12 S1 Med. Coating Aid leiicies Mottle tudinalOPCT 0 M S1" (25 it.) Streaks S1 81' Example 9 6 3 s1 S1. In a coatingexperiment similar to that described 111'- the preceding example,N-2,4-di(t -amyl)phenoxyacetyl- N-cyclohexyltaurine, sodium salt (ACT),was used as the coating aid. The following results Wereobtained:

7 Example 5 In a coating run similar to that described in Example 3 inwhich N-p-t.-octylpheiioxyacetylglycyl N-methyltau l R L rine, sodiumsalt (OPGMT), was used as the coating aid; Coating Aidv 325 ifi thefollowing results were obtained: v (25 ft.) Streaks R 1 7 L n rol 12 MedCoating Aid len e ies Mottle tiidir ial T 0 (25it. Streaks V g t i V Theoccurrence of pencil line streaks is a persistent de-SFfiri:::::::::::::::::I:: 3 sii 'i'r'ciII El: fact wallngs achieved bythe Simultaneous l r t fi e of two gelatin layers to a filmbase orpaper. The ability Example 6 of a coating aid to reduce the incidence ofpencil line In a coating experiment in which both a photographic sioncontaining the coating aid has a spread of about 5 cm. when coated in astandard manner on a soap-cleaned, plied to paper by a multiple hoppercoating technique as horizontal surface of a highly polished stainlesssteel described in US. Patent No. 2,76l,99l-using N'-p-t.- 0ctylplate. iphenoxyacetyl-N-methyltaurine, sodium salt (OPT), com- We claim:

pared to a standard in which a mixture of two coating ,75

In a coating experimentsimilarto, that described in Exsodium salt(OPCT), was used as thecoating aid. The

streaks is indicated when 1 ml. of a photographic emul-= 1. Acompositionof matter comprising gelatin cone.

' )n In which R is branched alkyl, (R) totals 8 to 16 carbon atoms, n isan integer of 1 to 2, Q is selected from the group consisting of a bondand C--HNCH2 I; R is selected from the group consisting of alkyls of 1to 4 carbon atoms and cycloalkyl, and M is a substituent selected fromthe group consisting of Na, K, Li, NH, and alkylammonium. 2. Acomposition of matter comprising gelatin containing coating aidcorresponding to the following formula:

In which R is branched alkyl of 8 to 16 carbon atoms and R is selectedfrom the group consisting of alkyls of 1 to 4 carbon atoms andcycloalkyl. 4. A gelatin-silver halide photographic emulsion containinga coating aid corresponding to the following for- (Rh it 6 In which R isbranched alkyl, (R) n totals 8 to 16 carbon atoms, n is an integer of 1to 2, Q is selected from the group consisting of a bond and R isselected from the group consisting of alkyls of 1 to 4 carbon atoms andcycloalkyl,

and M is a substituent selected from the group consisting of Na, K, Li,NH, and alkylammonium.

5. A composition of matter comprising gelatin containing therein as acoating aid the sodium salt ofN-ptert.-octylphenoXyacetyl-N-cyclohexyltaurine.

6. A gelatin-silver halide photographic emulsion containing therein as acoating aid the sodium salt ofN-ptert.-octylphenoxyacetyl-N-cyclohexyltaurine.

7. A composition of matter comprising gelatin containing therein as acoating aid the sodium salt ofN-ptert.-octylphenoxyacetyl-N-methyltaurine.

8. A gelatin-silver halide photographic emulsion containing therein as acoating aid the sodium salt ofN-ptert.-octylphenoxyacetyl-N-methyltaurine.

9. A composition of matter comprising gelatin containing therein as acoating aid the sodium salt of N-pentadecylphenoxyacetyl-N-methyltaurine.

10. A composition of matter comprising gelatin containing therein as acoating aid the sodium salt of N-p-.tert.-octylphenoxyacetylglycyl-N-methyltaurine.

, 11. A composition of matter comprising gelatin containing therein as acoating aid the sodium salt of N-2,4- di (tert.amyl)phenoxyacetyl-N-cyclohexyltaurine.

References Cited in the file of this patent UNITED STATES PATENTS2,739,891 Knox et al Mar. 27, 1956 2,823,123 Knox et al. Feb. 11, 19582,899,327 Christopher et a1 Aug. 11, 1959 2,933,406 Salzberg et a1 Apr.16, 1960 3,003,877 McLaughlin et al Oct. 10, 1961 3,026,202 Knox et al.Mar. 20, 1962 3,038,804 Knox et al. June 12, 1962 3,042,522 Ben-Ezra etal. July 3, 1962 3,068,101 Knox et al. Dec. 11, 1962

4. A GELATIN-SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING A COATINGAID CORRESPONDING TO THE FOLLOWING FORMULA: